201226555 六、發明說明： 【發明所屬之技術領域】 本發明涉及一種含羥胺的清洗液及其應用。 【先前技術】201226555 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a cleaning solution containing hydroxylamine and its use. [Prior Art]
在半導體元器件製造過程中，光阻層的塗敷、曝光和 器件的_製造來說是必工藝步驟。在_化的最後（= 阻層的塗敷、成像、離子植入和_之後）進行下一玉藝步驟之於， 光阻層材料的前物f徹絲去。在_步财離子A擊會硬^ 阻層聚合物，因此使得光崎變得不易溶解從^更難於除去。至八 在半導體製造工業中-般使用兩步法（乾法灰化和濕姓刻）除去這 層光阻層膜。第-步_乾法灰化除絲阻層（pR)的大部分； 第二步_祕·合物祕挪清缸祕去且清洗細餘的光 阻層’其步驟-般為清洗液清洗/漂洗/去離子水漂洗。在這個過程 中八犯除去殘留的聚合物光阻層和無機物，而不能攻擊損害金屬層 如紹層。 ， 在目前的濕法清洗工藝中，用得最多的清洗液是含有瓣類的 清洗液，這類清洗液目前主要是有EKC和ACT兩家公司開發，並佔 有較大的市場份額。其典型的專利有US611〇881、US6319885、 US5672577、US6030932、US6825156 和 1^5419779等。這類清洗 液的主要特徵是使用鄰苯二酚作為其主要組分之一；而鄰苯二酚是 201226555 有毒物質，在許多國家已經開始限制使用。所以隨著環保意識增 強’越來越麵公司希望_不含轉二_含練溶液去進行光 阻層材料的殘留物去除，以保證操作人員的健康和較好運營環境。 【發明内容】 本發明的目岐克服現有技術中存在的上述缺陷。提供一種較 為環保的含Μ㈣清洗液’該清洗液雜了傳贿_清洗液的清 洗能力，同時對金屬和非金屬的腐蝕速率較小。 本發明清洗液含有： 1) 溶劑：10〜80 %; 2) 水：10〜45%; 3) 羥胺：1〜40%; 4)硫醇苯並噻唑類有機物：0丨〜⑺％; 本發明中，所述的溶劑可選自亞碾、碾、咪魏明吻各烧嗣 咪唾侧，、醯胺和醇胺中的—種或多種，優選醇胺。盆中，戶 述的亞砜較佳的為二甲細;所述的砜較佳的為環丁颯:聰 ♦細較佳的為咪饿_;所_对_較化 為N-曱基吡咯烷酮；所述的咪唑啉酮較佳的為1 3 — , 啉酮（DMI);所述的醯胺較佳的為二 ，甲基咪4 土甲酿胺，所述的喊較+ 的為丙二醇單曱醚、二丙二醇單甲醚。 f ^ ^ W所4的醇胺較佳的為單乙g 胺、一乙醇胺、二乙酵胺、異内醇胺、2_广- -、二乙氨基）乙醇、 二乙醇胺和二甘醇胺。 201226555 本發明還進一步包含水。 本發明還進一步包含羥胺。 下結構 在本發明中’所述的硫醇苯並嗟u坐類有機物是扑人 的有機物。 'In the fabrication of semiconductor components, the application of photoresist layers, exposure and device fabrication are mandatory steps. At the end of the _ization (= coating of the resist layer, imaging, ion implantation, and _), the next jade step is performed, and the precursor of the photoresist layer material is cut away. In the _ step, the ion A hits the hard layer of the polymer, thus making it difficult for the light to be dissolved from ^ to be more difficult to remove. To eight In the semiconductor manufacturing industry, this two-layer photoresist film is removed by a two-step method (dry ashing and wet etching). The first step _ dry ashing the majority of the wire repellent layer (pR); the second step _ secret · compound secret clear the cylinder secret and clean the residual photoresist layer 'the steps - generally clean the cleaning solution / rinse / deionized water rinse. In this process, the eight photoresists remove the residual polymer photoresist layer and inorganic substances, and cannot attack the damaged metal layer such as the layer. In the current wet cleaning process, the most used cleaning fluid is a cleaning fluid containing petals. Currently, these cleaning fluids are mainly developed by EKC and ACT, and have a large market share. Typical patents are US611〇881, US6319885, US5672577, US6030932, US6825156 and 1^5419779. The main feature of this type of cleaning fluid is the use of catechol as one of its main components; catechol is 201226555 toxic substance, which has been restricted in many countries. Therefore, with the increasing awareness of environmental protection, more and more companies hope that _ does not contain the second _ containing the solution to remove the residue of the photoresist layer material to ensure the health of the operators and better operating environment. SUMMARY OF THE INVENTION The object of the present invention overcomes the above-discussed deficiencies in the prior art. Providing a more environmentally friendly ruthenium (iv) cleaning solution. The cleaning solution is a mixture of the cleaning ability of the bribe _ cleaning solution, and the corrosion rate of metal and non-metal is small. The cleaning solution of the invention comprises: 1) solvent: 10~80%; 2) water: 10~45%; 3) hydroxylamine: 1~40%; 4) mercaptan benzothiazole organic: 0丨~(7)%; In the invention, the solvent may be selected from the group consisting of a sub-mill, a mill, a mussel, a saliva, a mercaptoamine and an alkanolamine, preferably an alkanolamine. In the pot, the sulfoxide of the household is preferably dimethyl sulphate; the sulfone is preferably cyclobutanil: the succinct is preferably fine, and the sulfonate is N-mercapto. Pyrrolidone; the imidazolidinone is preferably a 1,3- nal ketone (DMI); the guanamine is preferably a dimethylamine 4, and the singularity is + Propylene glycol monoterpene ether, dipropylene glycol monomethyl ether. The alcohol amine of f ^ ^ W is preferably monoethylamine, monoethanolamine, diethylamine, iso-alkolamine, 2-poly-, diethylamino)ethanol, diethanolamine and diglycolamine. . 201226555 The invention still further comprises water. The invention still further comprises hydroxylamine. Lower structure In the present invention, the thiol benzopyrene-based organic substance is an organic substance. '
HS— SHS-S
其中：取代基R卜R2，R3，R4可以獨立地為氣原子，經基， 硫醇基，敌基、確酸基、C1-C6的有機取代基。優選R1，幻，r1， R4中有兩個或兩個以上的取代基為羥基的硫醇笨並噻唑類有機 物。 本發明的清洗液由上述成分簡單均勻混合即可製得。 本發明的清洗液用於去除光阻層殘留物，在用光阻清洗液去除 晶圓上刻蝕殘餘物以後，之後漂洗並乾燥即可。 本發明的積極進步效果在於··通過加入硫醇苯並噻唑類有機 物，成功地替代了傳統羥胺類清洗液中使用的有毒物質鄰苯二酚， 保留了目前羥胺類清洗液較強的清洗能力，同時對金屬和非金屬的 腐蝕速率較小；對環境較為友善，有利於保證操作人員的健康和較 好運營環境。 201226555 【實施方式】 下面用實施例來進一步說明本發明。 實施例1〜20 表1實施例1~2〇 實施例 溶劑 羥胺 去離子 水 硫醇苯並噻唑類有機物 名稱 含量 wt% 含量 wt% 含量 wt% 取代基 R1 取代基 R2 取代基 R3 取代基 R4 含 量wt% 1 二甲基 亞颯 10 40 45 羥基 羥基 羧基 磺酸基 5 2 環丁諷 15 35 40 羥基 羥基 磺酸基 羥基 10 3 1，3·二 甲基-2-咪唑烷 酮 80 1 19.9 氫原子 磺酸基 氫原子 氫原子 0.1 4 N-甲基 吡咯烷 酮 79.8 10 10 氫原子 氫原子 氫原子 氫原子 0.2 5 1，3-二 甲基-2-咪唑啉 酮 50 5 34.5 硫醇基 羧基 硫醇基 羧基 0.5 6 二甲基 甲醯胺 54.2 15 30 甲基 羥基 羥基 氫原子 0.8 7 丙二醇 單甲醚 53.5 20 25 己羧基 乙羧基 羥基 羥基 1.5 8 二丙二 醇單甲 醚 35 25 38 磺酸基 硫醇基 羥基 羥基 2 9 二乙醇 胺 36 30 30 羥基 乙基 硫醇基 羧基 4 10 單乙醇 胺 69 15 15 羥基 羥基 羧基 甲氧基 1 11 異丙醇 胺 45 23 25 羥基 羥基 羥基 氫原子 7 12 三乙醇 胺 40 25 30 羥基 羥基 羥基 己羧基 5 201226555Wherein: the substituent R, R2, R3, and R4 may independently be a gas atom, a thiol group, an aryl group, an acid group, or an organic substituent of C1-C6. Preferred are thiol benzothiazoles having two or more substituents of R1, phantom, r1, and R4 which are hydroxyl groups. The cleaning liquid of the present invention can be obtained by simply and uniformly mixing the above components. The cleaning solution of the present invention is used to remove the photoresist residue, and after removing the etching residue on the wafer with the photoresist cleaning solution, it is then rinsed and dried. The positive progress of the invention is that the toxic substance catechol which is used in the traditional hydroxylamine cleaning liquid is successfully replaced by adding the thiol benzothiazole organic substance, and the cleaning ability of the current hydroxylamine cleaning liquid is retained. At the same time, the corrosion rate of metal and non-metal is small; the environment is friendly, which is beneficial to ensure the health of operators and better operating environment. 201226555 [Embodiment] Hereinafter, the present invention will be further described by way of examples. Examples 1 to 20 Table 1 Examples 1 to 2 〇 Examples Solvent Hydroxylamine Deionized Water Thiol Benzothiazole Organics Name Content wt% Content wt% Content wt% Substituent R1 Substituent R2 Substituent R3 Substituent R4 Content Wt% 1 dimethyl hydrazine 10 40 45 hydroxy hydroxy carboxy sulfonate 5 2 cycline 15 35 40 hydroxy hydroxy sulfonic acid hydroxy 10 3 1,3 · dimethyl-2-imidazolidinone 80 1 19.9 hydrogen Atomic sulfonic acid hydrogen atom hydrogen atom 0.1 4 N-methylpyrrolidone 79.8 10 10 hydrogen atom hydrogen atom hydrogen atom hydrogen atom 0.2 5 1,3-dimethyl-2-imidazolidinone 50 5 34.5 thiol carboxy thiol Carboxyl group 0.5 6 dimethylformamide 54.2 15 30 methylhydroxyl hydrogen atom 0.8 7 propylene glycol monomethyl ether 53.5 20 25 hexylcarboxyethyl hydroxyhydroxyl group 1.5 8 dipropylene glycol monomethyl ether 35 25 38 sulfonate thiol group Hydroxyhydroxy 2 9 Diethanolamine 36 30 30 Hydroxyethylthiolcarboxyl 4 10 Monoethanolamine 69 15 15 Hydroxyhydroxycarboxymethoxy 1 11 Isopropanolamine 45 23 25 Hydroxyhydroxyl Hydrol Atom 7 12 Triethanolamine 40 25 3 0 hydroxy hydroxy hydroxy hexyl carboxyl group 5 201226555
率並對三種― 溶液的金屬腐蝕速率測試方法. (Rsl); 〇利用NaPS〇n四點探針儀測試4*4⑽呂空白石夕片的電阻初值 V· 2) 將該4 4cm鋁空白矽片浸泡在預先已經恒溫到設定溫度的溶 液中60分鐘； 3) 取出該4*4cm銘空白石夕片，漂洗後高純氤氣吹乾，再利用 Napson四點探針儀測試4*4Cm鋁空白矽片的電阻值（Rs2); 201226555 4)把上述電阻值和浸泡時間輸入到合適的程式可計算出其腐 姓速率。 溶液的非金屬腐蝕速率測試方法： 1) 利用Nanospec6100測厚儀測試4*4cm PETEOS石夕片的厚戶 (T1)； 2) 將該4*4cmPETEOS矽片浸泡在預先已經恒溫到設定溫度的 溶液中60分鐘； 3) 取出該4*4cmPETEOS矽片’漂洗後高純氮氣吹乾，再利用Rate and test method for metal corrosion rate of three kinds of solution. (Rsl); 测试 Test the initial value of resistance of 4*4(10) Lu blank Shixi tablets by NaPS〇n four-point probe instrument V· 2) The bracts are immersed in a solution that has been previously thermostated to a set temperature for 60 minutes; 3) Remove the 4*4 cm blank Shishixi tablets, rinse with high-purity helium, and test 4*4Cm with a Napson four-point prober. Resistance value of aluminum blank ( (Rs2); 201226555 4) Enter the above resistance value and immersion time into the appropriate program to calculate the rate of rot. Test method for non-metallic corrosion rate of solution: 1) Test the thickened household (T1) of 4*4cm PETEOS Shixi tablets with Nanospec6100 thickness gauge; 2) Soak the 4*4cm PETEOS tantalum sheet in a solution that has been previously thermostated to the set temperature 60 minutes; 3) Take out the 4*4cm PETEOS 矽 piece, rinse with high-purity nitrogen, and reuse
Nanospec6100測厚儀測試4*4cmPETEOS矽片的厚度（T2); 4) 把上述厚度值和浸泡時間輸入到合適的程式可計算出其腐 餘速率。 晶圓清洗的方法： 1) 將待清洗的晶圓放入預先已經恒溫到設定溫度的溶液中； 2) 按照金屬線浸泡20分鐘、通道和金屬墊浸泡3〇分鐘的原則 浸泡晶圓； 3) 浸泡時間到後，取出該晶圓，漂洗後高純氮氣吹乾；送SEm 測試。 表2部分實施例性能測試結果一覽 實施例 金屬(鋁）的腐 蝕速率，A/min 非金屬(等離子 體增強的二氧 化砂，PETEOS) 的腐蝕速 率，，A/min 不同類型晶圓清洗結果 金屬線 通道 金屬墊 8 <2 <0.5 乾淨，無腐蝕 乾淨通道 尺寸未改變 乾淨，無 腐蝕 201226555 2.69 <0.5 _乾淨，基本無-腐触 乾淨·ϊΐϋ 尺寸未改變 乾淨，基 本無腐蝕 <2 <0.5 乾淨，無腐鈾 尺寸未改變 淨，無 腐蝕 <2 <0.5 乾淨，無腐蝕 乾淨’職 尺寸未改變 乾淨，無 腐蝕 <2 <0.5 乾淨’無腐蝕 乾淨，通J1 尺寸未改變 乾淨，無 腐蝕 <2 <0.5 乾淨，無腐蝕 尺寸未改變 $淨，無 腐触 19 . s n本發_清洗敝合物解導體製成中所 龜μ (如金屬⑷和非金屬（如航咖）基本不會韻，其 溶液對部分小於轉縣界通常所要_埃每分鐘。用該 去除’ ^刊崎物進行清洗發現，其等離子·殘留物均被 的金屬和非^齡屬和非金屬。說明本發明的清洗有較低 晶圓進行清Γ 率，同時能對金屬線、通道和金屬墊三種 练上，本發明的積極進步效果在於： 力半1二了:ΓΓΓ並保持了傳統_類清洗液的清洗能 境^導體明IU洗液。有利於保證操作人員的徤康和較好運營環 2)其對金屬和非金屬的腐蝕速率較小。 【圖式簡單說明】 (無） 【主要元件符號說明】 (無）The Nanospec6100 Thickness Gauge tests the thickness of the 4*4cm PETEOS® (T2); 4) Enter the thickness and soak time into the appropriate program to calculate the decay rate. Wafer cleaning method: 1) Put the wafer to be cleaned into a solution that has been previously thermostated to a set temperature; 2) soak the wafer according to the principle of immersing the wire for 20 minutes, soaking the channel and the metal pad for 3 minutes; After the immersion time is reached, the wafer is taken out, rinsed with high-purity nitrogen gas, and sent to the SEm test. Table 2 Partial Examples Performance Test Results at a Glance Example Metal (Aluminum) Corrosion Rate, A/min Non-Metal (Plasma Enhanced Silica Sand, PETEOS) Corrosion Rate, A/min Different Types of Wafer Cleaning Results Metal Line channel metal pad 8 < 2 <0.5 Clean, non-corrosive clean channel size has not changed clean, no corrosion 201226555 2.69 <0.5 _ clean, basically no-corrosion clean · ϊΐϋ size has not changed clean, basically no corrosion < 2 <0.5 clean, non-corrosive uranium size has not changed net, no corrosion <2 <0.5 clean, no corrosion clean 'service size has not changed clean, no corrosion <2 <0.5 clean 'no corrosion clean, pass J1 The size has not changed clean, no corrosion < 2 < 0.5 clean, no corrosion size has not changed $ net, no corrosion touch 19. sn hair _ cleaning 敝 compound conductor made in the turtle μ (such as metal (4) and non Metals (such as aviation coffee) are basically not rhyme, and the solution is partially smaller than the average of the county. It is usually used every minute. It is cleaned with the removal of 'Ziqi', and its plasma and residue are metal and The age of the invention is non-metallic. It shows that the cleaning of the present invention has a lower wafer cleaning rate, and can be applied to the metal wire, the channel and the metal pad. The positive progress of the invention is as follows: ΓΓΓ 保持 保持 保持 保持 保持 保持 保持 保持 保持 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁 清洁[Simple description of the diagram] (None) [Description of main component symbols] (none)